CN101250199A - Method for preparing diisopropyl phosphite - Google Patents
Method for preparing diisopropyl phosphite Download PDFInfo
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- CN101250199A CN101250199A CNA2008100200500A CN200810020050A CN101250199A CN 101250199 A CN101250199 A CN 101250199A CN A2008100200500 A CNA2008100200500 A CN A2008100200500A CN 200810020050 A CN200810020050 A CN 200810020050A CN 101250199 A CN101250199 A CN 101250199A
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- diisopropyl phosphite
- phosphorus trichloride
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Abstract
The invention relates to a method for preparing diisopropyl phosphate via the esterification of phosphorus trichloride and isopropanol, which comprises adding phosphorus trichloride into benzene solvent to form a first mixture, adding benzene, isopropanol and weak alkaline organic catalyst into a reactor to form a second mixture, slowly adding the first mixture into the second mixture to form a reaction system, increasing and controlling temperature, reacting for 4.5-9h to obtain the mixture containing diisopropyl phosphate, deacidifying the mixture via pure alkali, filtering, distilling, depressurizing and distilling to obtain final diisopropyl phosphate product. The preparation method has low cost and high yield.
Description
Technical field
The present invention relates to a kind of preparation method of phosphorous acid ester.
Background technology
Phosphorous acid ester and phosphoric acid ester all are the intermediates of preparation organophosphorus pesticide.When preparing (Asia) phosphoric acid ester at present, generally all adopt phosphorus trichloride, phosphorus oxychloride or phosphorus thiochloride and alcohols (as methyl alcohol, ethanol) or phenols (as phenol) to carry out esterification, hydrogenchloride and other muriate are emitted in reaction; The mixture that contains liquid hydrogenchloride and thick ester that reaction generates obtains (Asia) phosphoric acid ester crude product after (promptly this mixture flows into the depickling jar after the condenser cooling, through heating, depickling) handled in depickling.Crude product promptly obtains the pure product of (Asia) phosphoric acid ester accordingly through vacuum fractionation again.This preparation method is because esterification reaction product just cools off by condenser, so speed of cooling is slow, and resultant of reaction also can dissolve a large amount of hydrogenchloride in temperature-fall period, thereby increased side reaction.Moreover, in deacidification, need could remove de-chlorine hydride, and can increase side reaction when heating up by heating, also can lose part (Asia) phosphoric acid ester simultaneously, thereby influence the yield of (Asia) phosphoric acid ester.Zhi Bei its yield of (Asia) phosphoric acid ester is usually 70～80% as stated above.
Diisopropyl phosphite is a kind of in the phosphorous acid ester, is mainly used in the intermediate of antiviral and is used for additive on the petrochemical complex, and in addition, it also is widely used in treating cardiovascular disease and cosmetic industry.In the prior art, diisopropyl phosphite is to adopt above-mentioned preparation method's preparation, and yield is lower.
The patent No. discloses a kind of method for preparing phosphorous acid ester for the Chinese invention patent of " 02146607.6 ", this method adopts in esterification reaction process, the mixed solution that feeding is made up of the salt of weak acid and the phosphorous acid ester of ammonium cools off reaction system, to weaken the Decomposition of hydrogenchloride to phosphoric acid ester, and adopt logical ammonia depickling to guarantee the yield of phosphorous acid ester, prepare diisopropyl phosphite by this method, it is at first to obtain phosphorous acid ester with other method that the mixed solution that the salt of weak acid of employing ammonium and phosphorous acid ester are formed carries out the refrigerative prerequisite to reaction system, bring the loaded down with trivial details of the raising of cost and operation undoubtedly, in addition, adopt logical ammonia depickling, though can guarantee yield to a certain extent, equipment cost is higher.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of diisopropyl phosphite in order to overcome the deficiencies in the prior art, and this preparation method's production cost is low, yield is high.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of diisopropyl phosphite adopts phosphorus trichloride and Virahol to carry out esterification and synthesizes, and it is characterized in that: this preparation method comprises the steps:
(1), under 0～10 ℃, phosphorus trichloride joined and form first mixed solution in the benzene solvent;
(2), in reactor, add benzene, Virahol and weakly alkaline organic catalyst, form second mixed solution, keep second mixed solution described first mixed solution to be made the formation reaction system slow the adding at 0～10 ℃, the adding speed of described first mixed solution is smaller or equal to 200kg/h, after treating that described first mixed solution adding finishes, be incubated 1～2h down at 0～10 ℃; Then reaction system slowly is warming up to 15～35 ℃, and under this temperature insulation reaction 1.5～3h; At last reaction system is continued slowly to be warming up to backflow, obtain comprising the compound of diisopropyl phosphite behind the 2～4h that refluxes;
(3), will cool off to room temperature through the described compound that step (2) obtain, in changing over to and in the still, keep slowly adding soda ash under 5～15 ℃ of the compounds and be neutralized to PH for neutral, soda ash is excessive a little;
(4), will and collect filtrate through the compound press filtration of step (3), gained filtrate obtains described diisopropyl phosphite through distillation, underpressure distillation.
The weakly alkaline organic catalyst is preferably triethylamine.
The ratio of the amount of substance of Virahol, phosphorus trichloride, triethylamine preferred 1: 0.3～0.4: 0.9～1.1.In the step (1) in first mixed solution quality percentage composition of phosphorus trichloride be 30%～40%.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
The present invention at first is dissolved in phosphorus trichloride in the solvent benzol, and then slowly joins and be dissolved with in the solution that another reactant is a Virahol, makes to reduce side reaction by the esterification rapid heat dissipation.
When esterification, add the weakly alkaline catalyzer, the hcl reaction that generates in weakly alkaline catalyzer and the reaction process, the direction that helps reacting towards product is carried out on the one hand, can reduce on the other hand because the generation of the side reaction that hydrogenchloride causes;
Owing to use benzene solvent, and, can reduce the meltage of hydrogenchloride without methanol solvate, reduce side reaction, benzene can also be recycled simultaneously, reduces production costs;
In the depickling step, adopt the excessive a little soda ash of adding to neutralize, the less water that may contain in the compound can be removed simultaneously, guarantee that distillation and rectifying obtain highly purified diisopropyl phosphite finished product;
The preparation method of diisopropyl phosphite of the present invention is owing to reduce the generation of by product, and yield height, production cost are low, simple to operate.
Embodiment
Below the specific embodiment of the present invention is described:
Preparation method according to the diisopropyl phosphite of present embodiment in turn includes the following steps:
(1), 360kg benzene is dropped in the 1000L batching still, chuck is opened freezing, and controlled temperature suction phosphorus trichloride 200kg slowly under 7～9 ℃ is made into first mixed solution, and a suction high position is stand-by.
(2), 360kg benzene, 240kg Virahol and 404kg triethylamine dropped in the reactor of 2000L and form second mixed solution, second mixed solution is cooled to 7～10 ℃, under this temperature, slowly first mixed solution is added, three h drip off.Drip and finish, with reaction system insulation reaction 1h under this temperature; Slowly be warming up to 20～30 ℃ of insulation reaction 2h then, (intensification must be slow, and the holding stage temperature rises in proportion with the time from low to high, and insulation is 30 ℃ at last extremely.) the insulation end, slowly heat up again (must be slow, there are a large amount of hydrogen chloride gas to produce, to absorb with device for absorbing tail gas) until backflow, when reaching 70 ℃, reflux temperature begins to calculate reflux time, behind the 3h, finish reaction, obtain containing the compound of diisopropyl phosphite.
(3), will cool off to room temperature through the compound of step (2), in the suction and in the still, open at chuck under the situation of water coolant, promptly keep 5～10 ℃ of compounds slowly to add soda ash and be neutralized to PH for neutral.Soda ash is excessive a little, and the soda ash consumption is 65～75kg, to reach dehydrating effect.
(4), after neutralization finishes, by surge pump, pressure filter press filtration, (filter cake is with reclaiming the benzene rinsing in right amount, and merging filtrate) the benzene still takes off in filtrate going into, and steams slide, and first normal pressure steams benzene, originally eliminate until phenyl, decompression is steamed to eliminate benzene and is obtained thick ester 210～230kg (reclaim benzene analyze moisture content be used for following crowd after qualified and apply mechanically) again, and behind the sampling analysis, underpressure distillation obtains content greater than diisopropyl phosphite finished product 135～140kg of 99.0% again.
Claims (4)
1, a kind of preparation method of diisopropyl phosphite adopts phosphorus trichloride and Virahol to carry out esterification and synthesizes, and it is characterized in that: this preparation method comprises the steps:
(1), under 0～10 ℃, phosphorus trichloride joined and form first mixed solution in the benzene solvent;
(2), in reactor, add benzene, Virahol and weakly alkaline organic catalyst, form second mixed solution, keep second mixed solution at 5～10 ℃, the slow adding of described first mixed solution is wherein obtained the reaction system of esterification, the adding speed of described first mixed solution is smaller or equal to 200kg/h, after treating that described first mixed solution adding finishes, be incubated 1～2h down at 5～10 ℃; Then reaction system slowly is warming up to 15～35 ℃, and under this temperature insulation reaction 1.5～3h; At last reaction system is continued slowly to be warming up to backflow, obtain comprising the compound of diisopropyl phosphite behind the 2～4h that refluxes;
(3), will cool off to room temperature through the described compound that step (2) obtain, in changing over to and in the still, keep slowly adding soda ash under 5～15 ℃ of the compounds and be neutralized to PH for neutral, soda ash is excessive a little;
(4), will and collect filtrate through the compound press filtration of step (3), gained filtrate obtains described diisopropyl phosphite through distillation, underpressure distillation.
2, the preparation method of a kind of diisopropyl phosphite according to claim 1 is characterized in that: described weakly alkaline organic catalyst is a triethylamine.
3, the preparation method of a kind of diisopropyl phosphite according to claim 2 is characterized in that: the ratio of the amount of substance of described Virahol, phosphorus trichloride, triethylamine is 1: 0.3～0.4: 0.9～1.1.
4, the preparation method of a kind of diisopropyl phosphite according to claim 1 is characterized in that: in the step (1), the quality percentage composition of phosphorus trichloride is 30%～40% in described first mixed solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2008100200500A CN101250199B (en) | 2008-03-20 | 2008-03-20 | Preparation method of diisopropyl phosphite |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2008100200500A CN101250199B (en) | 2008-03-20 | 2008-03-20 | Preparation method of diisopropyl phosphite |
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| CN101250199A true CN101250199A (en) | 2008-08-27 |
| CN101250199B CN101250199B (en) | 2012-04-18 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102448971A (en) * | 2009-05-28 | 2012-05-09 | 施里特马克控股公司 | Process for the preparation of dialkyl phosphites |
| CN101775033B (en) * | 2010-01-19 | 2012-08-29 | 青岛大学 | Preparation method of phosphite ester by using dividing wall tower reaction rectification technique |
| WO2013053939A1 (en) | 2011-10-13 | 2013-04-18 | Straitmark Holding Ag | Method for the esterification of p-o components |
| US8829222B2 (en) | 2009-05-28 | 2014-09-09 | Straitmark Holding Ag | Process for the manufacture of dialkylphosphites |
| CN114349785A (en) * | 2022-01-18 | 2022-04-15 | 江苏极易新材料有限公司 | Synthetic method of isotridecyl phosphite |
| CN114573633A (en) * | 2022-02-23 | 2022-06-03 | 太仓市茜泾化工有限公司 | Preparation process of triisopropyl phosphate |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2066932A1 (en) * | 1991-04-29 | 1992-10-30 | Robert E. Rosen | Phosphousulfonate herbicides |
| CN1282653C (en) * | 2002-01-18 | 2006-11-01 | 贵州大学 | Fluoric alpha-aminoalkyl phosphonate with agricultural antiviral activity and its synthesis |
-
2008
- 2008-03-20 CN CN2008100200500A patent/CN101250199B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102448971A (en) * | 2009-05-28 | 2012-05-09 | 施里特马克控股公司 | Process for the preparation of dialkyl phosphites |
| US8802883B2 (en) | 2009-05-28 | 2014-08-12 | Straitmark Holding Ag | Method for the manufacture of dialkylphosphites |
| US8829222B2 (en) | 2009-05-28 | 2014-09-09 | Straitmark Holding Ag | Process for the manufacture of dialkylphosphites |
| CN101775033B (en) * | 2010-01-19 | 2012-08-29 | 青岛大学 | Preparation method of phosphite ester by using dividing wall tower reaction rectification technique |
| WO2013053939A1 (en) | 2011-10-13 | 2013-04-18 | Straitmark Holding Ag | Method for the esterification of p-o components |
| CN114349785A (en) * | 2022-01-18 | 2022-04-15 | 江苏极易新材料有限公司 | Synthetic method of isotridecyl phosphite |
| CN114349785B (en) * | 2022-01-18 | 2022-11-01 | 江苏极易新材料有限公司 | Synthetic method of isotridecyl phosphite |
| CN114573633A (en) * | 2022-02-23 | 2022-06-03 | 太仓市茜泾化工有限公司 | Preparation process of triisopropyl phosphate |
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| CN101250199B (en) | 2012-04-18 |
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